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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 271 records · Page 15

Structural and Valence State Modification of Cobalt in CoPt Nanocatalysts in Redox Conditions

Platinum is the primary catalyst for many chemical reactions in the field of heterogeneous catalysis. However, platinum is both expensive and rare. Therefore, it is advantageous to combine Pt with another metal to reduce cost while also enhancing stability. To that end, Pt is often combined with Co to form Co-Pt nanocrystals. However, dynamical restructuring effects that occur during reaction in Co-Pt ensembles can impact catalytic properties. In this study, model Co 2 Pt 3 nanoparticles supported on carbon were characterized during a redox cycle with two in situ approaches, namely X-ray absorption spectroscopy (XAS) and scanning transmission electron microscopy (STEM) using a multimodal microreactor. The sample was exposed to temperatures up to 500 °C under H 2 , and then to O 2 at 300 °C. Irreversible segregation of Co in the Co-Pt particles was seen during redox cycling and substantial changes of the oxidation state of Co were observed. After the H 2 treatment, a fraction of Co could not be fully reduced and incorporated into a mixed Co-Pt phase. Re-oxidation of the sample increased Co segregation, and the segregated material had a different valence state than in the fresh, oxidized sample. Furthermore, this in situ study describes dynamical restructuring effects in CoPt nano-catalysts at the atomic scale that are crucial to understand to improve the design of catalysts used in major chemical processes.

36 MATERIALS SCIENCE↗

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO 2 or Al 2 O 3 . NH 3 -TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO 2 gives softer coke and increases cumulative benzene yields by 25%, while Al 2 O 3 strongly decreases yields. H 2 -TPR and UV-visible and Raman spectroscopy show how the overcoats redisperse the MoO x precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27 Al-MAS NMR, MoO x redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Altogether, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying the unmodified structural characteristics using multiple modifications

This paper describes a procedure for estimating the free-free modal characteristics of a system by testing multiple constrained states. The procedure eliminates the influences of the constraints on the modal parameters and provides important information at the connection points. For very stiff or very flexible test articles, it is difficult to support the test article and to measure uncompromised modal parameters. The method described in this paper measures the forces and/or responses at constraint-connection points and uses a direct parameter estimation algorithm to calculate the system's free-free characteristics. These free-free characteristics retain the local information at the connection or boundary points, thereby including the important local high frequency residual effects in the modal model.

Barney, Patrick↗

Fabrication of 3D-printed copper based zinc anodes

The production of a porous copper-zinc structure includes providing copper ink, creating a 3D model of the porous copper-zinc structure, 3D printing the copper ink into a porous copper lattice structure using the 3D model, heat treatment of the porous copper lattice structure producing a heat treated porous copper lattice structure, surface modification of the heat treated porous copper lattice structure by nanowires growth on the heat treated porous copper lattice structure producing a heat treated porous copper lattice structure with nanowires, and electrodeposition of zinc onto the heat treated porous copper lattice structure with nanowires to produce the porous copper-zinc structure.

Zhu, Cheng↗

A new partitioning strategy for efficient re-analysis of large structural systems

A computational procedure is presented for the reanalysis of large unsymmetric structural systems. The procedure is based on a novel partitioning strategy in which the responses of both the original and modified structures are approximated by symmetric and antisymmetric response vectors, each obtained by using only a fraction of the degrees of freedom of the discrete model of the structure. The procedure is applied to linear static analysis of framed structures. Design modifications consisted of removing members, resulting in topologically unsymmetric structures. The efficient application of the procedure on sequential computers as well as on multiprocessor computers is discussed, and its effectiveness is demonstrated by means of two numerical examples.

Noor, Ahmed K.↗

Bismaleimides and related maleimido polymers as matrix resins

Significant processing and property improvements can be achieved by copolymerization of state-of-the-art bisimides with various vinyl stilbazole derivatives to give both fire resistance and high-temperature properties from hot-melt compositions. Significant improvement in mechanical properties is achieved through these modifications, which may make these new matrix resins ideal candidates for fireworthy secondary graphite composite structures. Phosphorous modifications of maleimido polymers through phosphonate structure and tricyclophosphazene derivatives provide families of new matrix resins for short-time applications in severe thermo-oxidative environments. With further research these may provide matrix resins for long-term thermo-oxidative stability of advanced composites at temperatures up to 400 to 500 C.

Parker, J. A.↗

In silico λ-dynamics predicts protein binding specificities to modified RNAs

Abstract RNA modifications shape gene expression through a variety of chemical changes to canonical RNA bases. Although numbering in the hundreds, only a few RNA modifications are well characterized, in part due to the absence of methods to identify modification sites. Antibodies remain a common tool to identify modified RNA and infer modification sites through straightforward applications. However, specificity issues can result in off-target binding and confound conclusions. This work utilizes in silico λ-dynamics to efficiently estimate binding free energy differences of modification-targeting antibodies between a variety of naturally occurring RNA modifications. Crystal structures of inosine and N6-methyladenosine (m6A) targeting antibodies bound to their modified ribonucleosides were determined and served as structural starting points. λ-Dynamics was utilized to predict RNA modifications that permit or inhibit binding to these antibodies. In vitro RNA-antibody binding assays supported the accuracy of these in silico results. High agreement between experimental and computed binding propensities demonstrated that λ-dynamics can serve as a predictive screen for antibody specificity against libraries of RNA modifications. More importantly, this strategy is an innovative way to elucidate how hundreds of known RNA modifications interact with biological molecules without the limitations imposed by in vitro or in vivo methodologies.

Biochemistry & Molecular Biology↗

Flight investigation of a structural mode control system for the XB-70 aircraft

A flight investigation of a structural mode control system termed identical location of accelerometer and force (ILAF) was conducted on the XB-70-1 airplane. During the first flight tests, the ILAF system encountered localized structural vibration problems requiring a revision of the compensating network. After modification, successful structural mode control that did not adversely affect the rigid body dynamics was demonstrated. The ILAF system was generally more effective in supersonic than subsonic flight, because the conditions for which the system was designed were more nearly satisfied at supersonic speeds. The results of a turbulence encounter at a Mach number of 1.20 and an altitude of 9754 meters indicated that the ILAF system was effective in reducing the vehicle's response at this flight condition. An analytical study showed that the addition of a small canard to the modal suppression system would greatly improve the automatic control of the higher frequency symmetric modes.

Lock, W. P.↗

The deep structure of lunar basins - Implications for basin formation and modification

Models for the crustal structure in the vicinity of nine impact basins, from an inversion of gravity and topographic data from the lunar nearside are presented. The models display a low-density nonmare crustal layer and a mare basalt layer, both of variable thicknesses. Assuming that topography in mare areas is isostatically compensated before the emplacement of mare basalts and that compensation of mare basalt units may be neglected, a decomposition of the gravity anomaly into contributions from Moho relief and mare fill is permitted. Minimum values for mare basalt thicknesses are obtained but because mare basalts and mantle material are similar in density, the thicknesses of the nonmare crust are estimated. An important constraint is the crustal thickness inferred from the Apollo 12 and 14 landing sites from seismic observations. The crustal thickness model indicates that the crust is thinner beneath each of the major nearside basins than in surrounding areas. New bounds on the volume of material ejected from each basin are derived. The geological implications of structural differences among basins for the processes of basin formation and modification are evaluated as functions of time on the moon.

Bratt, S. R.↗

Thermally-Conductive Metallic Coatings and Applications for Heat Removal on In-Space Cryogenic Vehicles

For large in-space cryogenic upper stages, substantial axial heat removal from a forward skirt by vapor-based heat interception may not be achieved by simple attachment methods unless sufficient thermal conductance from the skirt to the cooling fluid can be achieved. Preferable methods would allow for the addition of the cooling system to existing structure with minimal impact on the structure. Otherwise, significant modification to the basic structural design andor novel and complex attachment mechanisms with high effective thermal conductance are likely to be required. The approach being pursued by evolvable Cryogenics (eCryo) is to increase the thermal performance of a relatively simple attachment system by applying metallic or other thermally conductive material coatings to the mating surface area of the fluid channel where it is attached the skirt wall. The expectation of candidate materials is that the dramatic increase in conductivity of pure metals at temperatures close to liquid hydrogen vapor temperature will compensate for the reduced actual contact area typical of mechanical joints. Basic contact conductance data at low temperatures for candidate interface materials is required to enable the test approach. A test rig was designed at NASA Glenn Research Center to provide thermal contact resistance testing between small sample coupons coated with conductive material via electron beam evaporation, a low-temperature option that will not affect physical properties of base materials. Average coating thicknesses were 10 k. The test fixture was designed to mount directly to a cryocooler cold head within a vacuum test chamber. The purpose of this test was to determine qualitative contact conductance between various test samples. Results from this effort will be implemented in a sub-scale vapor-based heat interception test, where the applicability for increased heat removal on large structural skirts will be considered.

small scale testing↗

Effect of processing on Polymer/Composite structure and properties

Advances in the vitality and economic health of the field of polymer forecasting are discussed. A consistent and rational point of view which considers processing as a participant in the underlying triad of relationships which comprise materials science and engineering is outlined. This triad includes processing as it influences material structure, and ultimately properties. Methods in processing structure properties, polymer science and engineering, polymer chemistry and synthesis, structure and modification and optimization through processing, and methods of melt flow modeling in processing structure property relations of polymer were developed. Mechanical properties of composites are considered, and biomedical materials research to include polymer processing effects are studied. An analysis of the design technology of advances graphite/epoxy composites is also reported.

Source record↗

The role of optimization in structural model refinement

To evaluate the role that optimization can play in structural model refinement, it is necessary to examine the existing environment for the structural design/structural modification process. The traditional approach to design, analysis, and modification is illustrated. Typically, a cyclical path is followed in evaluating and refining a structural system, with parallel paths existing between the real system and the analytical model of the system. The major failing of the existing approach is the rather weak link of communication between the cycle for the real system and the cycle for the analytical model. Only at the expense of much human effort can data sharing and comparative evaluation be enhanced for the two parallel cycles. Much of the difficulty can be traced to the lack of a user-friendly, rapidly reconfigurable engineering software environment for facilitating data and information exchange. Until this type of software environment becomes readily available to the majority of the engineering community, the role of optimization will not be able to reach its full potential and engineering productivity will continue to suffer. A key issue in current engineering design, analysis, and test is the definition and development of an integrated engineering software support capability. The data and solution flow for this type of integrated engineering analysis/refinement system is shown.

Lehman, L. L.↗

Structural Reliability Analysis and Optimization: Use of Approximations

This report is intended for the demonstration of function approximation concepts and their applicability in reliability analysis and design. Particularly, approximations in the calculation of the safety index, failure probability and structural optimization (modification of design variables) are developed. With this scope in mind, extensive details on probability theory are avoided. Definitions relevant to the stated objectives have been taken from standard text books. The idea of function approximations is to minimize the repetitive use of computationally intensive calculations by replacing them with simpler closed-form equations, which could be nonlinear. Typically, the approximations provide good accuracy around the points where they are constructed, and they need to be periodically updated to extend their utility. There are approximations in calculating the failure probability of a limit state function. The first one, which is most commonly discussed, is how the limit state is approximated at the design point. Most of the time this could be a first-order Taylor series expansion, also known as the First Order Reliability Method (FORM), or a second-order Taylor series expansion (paraboloid), also known as the Second Order Reliability Method (SORM). From the computational procedure point of view, this step comes after the design point identification; however, the order of approximation for the probability of failure calculation is discussed first, and it is denoted by either FORM or SORM. The other approximation of interest is how the design point, or the most probable failure point (MPP), is identified. For iteratively finding this point, again the limit state is approximated. The accuracy and efficiency of the approximations make the search process quite practical for analysis intensive approaches such as the finite element methods; therefore, the crux of this research is to develop excellent approximations for MPP identification and also different approximations including the higher-order reliability methods (HORM) for representing the failure surface. This report is divided into several parts to emphasize different segments of the structural reliability analysis and design. Broadly, it consists of mathematical foundations, methods and applications. Chapter I discusses the fundamental definitions of the probability theory, which are mostly available in standard text books. Probability density function descriptions relevant to this work are addressed. In Chapter 2, the concept and utility of function approximation are discussed for a general application in engineering analysis. Various forms of function representations and the latest developments in nonlinear adaptive approximations are presented with comparison studies. Research work accomplished in reliability analysis is presented in Chapter 3. First, the definition of safety index and most probable point of failure are introduced. Efficient ways of computing the safety index with a fewer number of iterations is emphasized. In chapter 4, the probability of failure prediction is presented using first-order, second-order and higher-order methods. System reliability methods are discussed in chapter 5. Chapter 6 presents optimization techniques for the modification and redistribution of structural sizes for improving the structural reliability. The report also contains several appendices on probability parameters.

Grandhi, Ramana V.↗

Composition, Activity, and Stability of IrO x Oxygen Evolution Reaction Electrocatalysts

The oxygen evolution reaction (OER) is integral to several electrochemical energy conversion and storage technologies, including carbon dioxide reduction to value added fuels, nitrogen reduction to ammonia, reversible fuel cells, rechargeable metal−air batteries, and water electrolysis to produce hydrogen. Iridium oxide (IrO x ) is widely recognized as the benchmark OER catalyst for acidic environments. Despite widespread use of IrO x catalysts, most notably in proton-exchange membrane water electrolyzers (PEMWEs), a comprehensive understanding of the physicochemical properties of commercial catalysts and the impact of these properties on both the activity and stability of these catalysts is lacking. Here, we study commercial IrO x catalysts with different physicochemical properties, three nominally considered amorphous and three rutile, to elucidate how structural and compositional variations affect OER activity and stability. Utilizing standardized aqueous electrochemical protocols, time-resolved dissolution quantification using inductively-coupled plasma mass spectrometry, and physicochemical characterization, including multiple synchrotron X-ray techniques, we systematically correlate catalyst properties with OER performance and degradation behavior aided by principal component analysis (PCA). Our results demonstrate the general trend of amorphous IrO x having higher intrinsic activity but limited stability and crystalline rutile IrO 2 having lower activity but enhanced stability against dissolution. The trends within the amorphous and rutile catalyst groups correlate with inherent material properties, including phase composition and structure, crystallinity, particle size, surface area, and surface structure/chemistry. Notably, we identify a rutile catalyst with the largest crystallite/ domain sizes, moderate surface area, a small fraction of hydrous phase, and a favorable pore structure (trimodal distributions of pore sizes ranging from 2−5 nm) that exhibits the best balance between activity and stability among the six catalysts studied here. These findings illustrate a fundamental structure-governed trade-off between activity and stability and highlight the critical role of surface chemistry modification and structure engineering in IrO x catalyst optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

7-Deazaguanines in DNA: functional and structural elucidation of a DNA modification system

Abstract The modified nucleosides 2′-deoxy-7-cyano- and 2′-deoxy-7-amido-7-deazaguanosine (dPreQ0 and dADG, respectively) recently discovered in DNA are the products of the bacterial queuosine tRNA modification pathway and the dpd gene cluster, the latter of which encodes proteins that comprise the elaborate Dpd restriction–modification system present in diverse bacteria. Recent genetic studies implicated the dpdA, dpdB and dpdC genes as encoding proteins necessary for DNA modification, with dpdD–dpdK contributing to the restriction phenotype. Here we report the in vitro reconstitution of the Dpd modification machinery from Salmonella enterica serovar Montevideo, the elucidation of the roles of each protein and the X-ray crystal structure of DpdA supported by small-angle X-ray scattering analysis of DpdA and DpdB, the former bound to DNA. While the homology of DpdA with the tRNA-dependent tRNA-guanine transglycosylase enzymes (TGT) in the queuosine pathway suggested a similar transglycosylase activity responsible for the exchange of a guanine base in the DNA for 7-cyano-7-deazaguanine (preQ0), we demonstrate an unexpected ATPase activity in DpdB necessary for insertion of preQ0 into DNA, and identify several catalytically essential active site residues in DpdA involved in the transglycosylation reaction. Further, we identify a modification site for DpdA activity and demonstrate that DpdC functions independently of DpdA/B in converting preQ0-modified DNA to ADG-modified DNA.

59 BASIC BIOLOGICAL SCIENCES↗

Structural basis of RNA cap modification by SARS-CoV-2

The severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2), the causative agent of COVID-19 illness, has caused millions of infections worldwide. In SARS coronaviruses, the non-structural protein 16 (nsp16), in conjunction with nsp10, methylates the 5'-end of virally encoded mRNAs to mimic cellular mRNAs, thus protecting the virus from host innate immune restriction. We report here the high-resolution structure of a ternary complex of SARS-CoV-2 nsp16 and nsp10 in the presence of cognate RNA substrate analogue and methyl donor, S-adenosyl methionine (SAM). The nsp16/nsp10 heterodimer is captured in the act of 2'-O methylation of the ribose sugar of the first nucleotide of SARS-CoV-2 mRNA. We observe large conformational changes associated with substrate binding as the enzyme transitions from a binary to a ternary state. This induced fit model provides mechanistic insights into the 2'-O methylation of the viral mRNA cap. We also discover a distant (25 Å) ligand-binding site unique to SARS-CoV-2, which can alternatively be targeted, in addition to RNA cap and SAM pockets, for antiviral development.

59 BASIC BIOLOGICAL SCIENCES↗